Low-foaming, stain-removing agents for textiles

ABSTRACT

The present invention relates to liquid, low-foaming, spotremoving agents consisting of A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula R1-(O-CH2-CH2)x-(O-CH-CH2)y-OH wherein R1 represents a straightchained hydrocarbon having from 16 to 24 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and x and y represent integers of from 20 to 40, B. from 25 percent to 45 percent by weight of a substantially water-insoluble compound of the formula R2-(O-CH2-CH2)z-OH wherein R2 represents a straight-chained hydrocarbon having from 14 to 22 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and z represents an integer of from one to eight, C. from 2 percent to 10 percent by weight of a hydrotropic alkali metal salt of an alkylated benzenesulfonate, the the alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms, D. from 1 percent to 15 percent by weight of water, and E. from 2 percent to 50 percent by weight of organic solvents having boiling points between the temperatures of 50* C. and 350* C., said liquid, low-foaming spot-removing agent having a viscosity not exceeding 500 cP at a temperature of 20* C.

United States Patent [72] Inventors Markus Berg Dusseldorf, Holthausen; Josef Hartenstein, Hilden, Rhineland, both of Germany [21] Appl. No. 672,964 [22] Filed on. 5, 1967 [45] Patented Dec. 7, 1971 [73] Assignee 1-lenke1& Cie Gmbl-l Dusseldorf-Holthnusen, Germany [32] Priority Nov. 18,1966 [33] Germany [31 H 61018 [54] LOW-FOAMING, STAIN-REMOVING AGENTS FOR TEXTILES 5 Claims, No Drawings [52] U.S.Cl 252/153, 252/152, 252/161,252/l71 [51] lnt.Cl C1ld1/18, C1 ld H12 [50] Field of Search 252/89, 161, 162, 170, 171, 173;8/l42 [56] References Cited UNITED STATES PATENTS 2,717,824 9/1955 Avery 8/142 2,941,952 6/1960 Lewis et al.. 252/161 3,213,028 10/1965 252/89 3,382,285 5/1968 260/615 2,697,075 12/1954 252/170 2,965,678 12/1960 Sundberg et a1. 260/615 3,382,177 5/1968 Woodruff 252/89 FOREIGN PATENTS 159,335 10/1954 Australia 252/89 800,159 8/1958 Great Britain 252/89 Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis AlmrneyHamm0nd & Littell ABSTRACT: The present invention relates to liquid, lowfoaming, spot-removing agents consisting of A. from 25 percent to 45 percent by weight ofa water-soluble compound of the formula R,(OCH -CH ),(OCHCl-l ),,Ol-l wherein R represents a straight-chained hydrocarbon having from 16 to 24 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and x and y represent integers of from to 40, I

B. from 25 percent to percent by weight of a substantially water-insoluble compound of the formula R (O--CH -CH ),-OH wherein R represents a straightchained hydrocarbon having from 14 to 22 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and 2 represents an integer of from one to eight,

C. from 2 percent to 10 percent by weight of a hydrotropic alkali metal salt of an alkylated benzenesulfonate, the the alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms,

D. from 1 percent to 15 percent by weight ofwater, and

E. from 2 percent to percent by weight of organic solvents having boiling points between the temperatures of 50 C. and 350 C., said liquid, low-foaming spot-removing agent having a viscosity not exceeding 500 cP at a temperature of 20 C.

LOW-FOAMING, STAIN-REMOVING AGENTS FOR TEXTILES THE PRIOR ART It is well-known that grease-containing stains can in most cases be removed only incompletely by the usual washing process, at washing temperatures from 30 C. to 60 C., as specified for textiles of synthetic fibers, silk, wool or cotton fabrics finished with synthetic resin, as well as for fabrics of mixed cotton and synthetic fibers. This applies mainly to the soiled rims on collars and cuffs of shirts, blouses, smocks and the like. Neither can, especially persistant stains be removed completely from laundry items which can be subjected to washing by boiling in a single washing process. Therefore, it has been recommended prior to the actual washing to rub the heavily soiled spots of the textile articles with a paste consisting of a powdery detergent with water added, or with a special pastelike washing assistant, consisting for the most part of aqueous mixtures of raw anionic and nonionic detergents. The first-mentioned process did not prove successful at all in practice, whereas the past preparations of the prior art were frequently not sufficiently effective with regard to stubborn grease stains, in particular, to those caused by skin fat, lard, solidified vegetable fats and browned frying fats. This pertains, in particular, to those cases where the stains have not been washed out immediately and thus have worked themselves into the textile goods for a prolonged time. Furthermore, in most cases, the already known stain removing agents increase in an undesirable manner the tendency to develop foam in the washing liquor so that this may result in a foaming over of the liquor, when the laundry is done in drum washers, even if socalled foam-arresting detergents are used.

OBJECTS OF THE INVENTION An object of the present invention is to develop a spotremoving agent, which does not possess the indicated shortcomings and which, due to its low-viscosity, can be applied to the textile fabric easily and without additional rubbing.

Another object of the invention is the obtention of liquid, low-foaming spot-removing agents consisting of agents consisting of A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula wherein R represents a straight'chained hydrocarbon having from 16 to 24 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and x and y represent integers of from 20 to 40,

B. from 25 percent to 45 percent by weight of a substantially water-insoluble compound of the formula wherein R represents a straight chained hydrocarbon having from 14 to 22 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, and 2 represents an integer of from one to eight,

C. from 2 percent to l percent by weight of a hydrotropic alkali metal salt of an alkylated benzenesulfonate, the alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms,

D. from 0 percent to 15 percent by weight of water, and

E. from 2 percent to 50 percent by weight of organic solvents having boiling points between the temperatures of 50 C. and 350 C., said liquid, low-foaming spot-removing agent having a viscosity not exceeding 500 c? at a temperature of C.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention relates to a liquid, low-foaming spot-removing product, characterized by its content of:

A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula R.(0 .H.). 0 .-0H

wherein R, represents a straight, saturated or unsaturated alkyl radical containing from 16 to 24 carbon atoms, and x and y are integers of 20 to 40,

B. from 25 percent to 45 percent by weight of a compound,

substantially insoluble in water, of the formula wherein R is a straight, saturated or unsaturated alkyl radical having from 14 to 22 carbon atoms, and 2 represents an integer of one to eight,

C. from 2 percent to 10 percent by weight of a hydrotropic compound selected from the group of the alkylbenzenesulfonates, the alkyl groups of these containing from one to three carbon atoms,

D. from 0 percent to l5 percent by weight of water, and

E. organic solvents in such an amount all together not exceeding 50 percent by weight, so that the viscosity of the product does not amount to more than 500 c? at a temperature of 20 C.

The preparation of the alkoxylated compounds of the formulas:

is effected in the usual manner by reacting straight, saturated or unsaturated fatty alcohols or synthetic alcohols of the chain length indicated with ethylene oxide or propylene oxide in the known manner. In connection with the alkoxylated product of formula A, it is preferable to employ a straight chain alkanol having from l8 to 22 carbon atoms which is alkoxylated first with from 25 to 35 mols of ethylene oxide and thereafter with from 25 to 35 mols of propylene oxide. Customarily mixed saturated fatty alcohols are employed although. purified alcohols may likewise be utilized as well as unsaturated alcohols such as alkenols and alkadienols. With reference to the alkoxylated product of formula B similar alcohols can be employed. Preferably, mixtures of such alkylene oxide condensates are employed, wherein the alkyl radical R contains from 18 to 22 carbon atoms, and x and y represent integers of 25 to 35, and wherein the number 2 is selected so that on an average for every four carbon atoms in the alkyl chain of R not more than one glycol ether group is employed. If this ratio is substantially exceeded in direction toward a higher ethoxylation degree, the cleaning effectiveness of the agents will decline.

The organic solvents to be employed should have a boiling pointnot below 50 C. and not exceeding 350 C. For the usual handling of the agents, these organic solvents should be essentially physiologically harmless without developing any annoying odor. Suitable for this purpose are alcohols, such as alkanols, for example, ethanol, propanol, isopropanol, ethylhexanol, etc.; phenylalkanols, for example, methylphenylcarbinol; ether alcohols, such as diethyleneglycol, the monomethyl or monoethyl ether of ethylene or propylene glycol or glycerine diethyl ether; amino alcohols, such as mono-, dior triethanolamines. Ketones and ethers are also suitable, such as acetone, methylethylketone and cyclohexanone; dipropylether, diisopropylether and diisogutylether. Also suitable are carboxylic acid esters, such as ethyl acetate, propyl acetate or ethylene glycol diacetate; aliphatic and aromatic hydrocarbons such as benzene, methylcyclohexane, tetraline or decaline; as well as chlorinated hydrocarbons, such as trichloroethylene or carbon tetrachloride. Moreover, mixtures of the solvents mentioned are used to advantage.

The portion of the organic solvents should not exceed 50 percent by weight of the entire mixture. Preferably, it should amount to 5 percent to 30 percent by weight. The kind and amount of the solvent used within the quantitative range are without essential importance with regard to the cleaning effect and the foaming capacity. However, they do exert an influence on the viscosity and to a certain measure also on the resistance to cold of the product. The amount of the solvent should be chosen so that the product is still sufficiently liquid even at relatively low-temperatures, which factor is guaranteed when its viscosity does not exceed 500 c? at a temperature of 20 C.

To improve the clear solubility and the viscosity behavior at low temperatures, spot removing compositions of the invention contain, in addition, from 2 percent to percent preferably from 4 percent to 7 percent, by weight of hydrotropic compounds of the group of low-molecular weight alkali metal alkylbenzenesulfonates. Compoundssuitable for this purpose are the alkali metal salts of toluenesulfonic acid, xylenesulfonic acids, ethylbenzenesulfonic acids and isopropylbenzenesulfonic acids.

The water content of the spot-removing compositions of theinvention should not amount to more than percent by weight, preferably 1 percent to 10 percent by weight. It was discovered in a rather startling manner that the cleaning effectiveness of the agents is exceptionally intense when the indicated water content is observed in relation to grease soiled as well as mineral soiled articles.

The preparation of the spot-removing compositions according to the invention is carried out by simply admixing the individual components, with or without melting as required.

The spot-removing compositions distinguish themselves by an intense cleaning effectiveness, in particular, with regard to the persistent fatand oil-containing soiled items. Due to their low-viscosity, the penetration of the cleaning solution into the textile article to be cleaned is essentially facilitated so that even deep-seated spots can be treated with success. The spotremoving compositions react in a neutral manner, act as fiberprotecting agents and, consequently, they are also suitable for cleaning delicate fabrics. They possess foam-arresting properties so that the textiles treated with these agents can be washed with the usual moderately forming or low-foaming detergents in conventional household drum washers without any danger that the washing liquor might cause excess foaming. Moreover, the products have a good storability, particularly at temperatures ranging from +10 to 0 C. Any slight cloudiness, possibly occurring in the cold, will not affect the cleaning action, but will disappear entirely when the product is restored to room temperature. With regard to this fact, the agents distinguish themselves favorably from numerous known liquid detergents, which during storage in the temperature range indicate either the tendency to have the components of the mixture separate or to develop a sedimentation. Such prior art products after reheating can be homogenized only with difficulty or not completely.

The following specific examples are illustrative of the spotremoving compositions of the invention. They are not to be deemed, however, as limitative in any respect.

EXAMPLES 1n the following the compositions of the several products are given in percent by weight. The abbreviations E0 and PrO mean the amount of added ethylene oxide or propylene oxide per me]. The admixing of the components to form the spotremoving compositions of the invention is effected in that first of all the xylenesulfonate is dissolved by heating in the water content specified, followed by the addition of the remaining components in liquid or melted form. All of the preparations were clear liquids at room temperature. The viscosities were determined by means of a Brookfield rotating viscosimeter using a No. 2 spindle at a temperature of C.

The foam behavior was studied under conditions closely re lated to actual practice. For this purpose, collars and cufis of soiled shirts or soiled colored Diolene" cotton mixed fabrics, soiled with oil and grease stains, were treated with the liquid preparations and washed in a washing machine as usually used in the household, with a horizontal drum, employing a lowfoaming detergent customarily used in machine washing in the usual procedure. The low-foaming detergent utilized was that of example 8 of DAS 1,080,250. This detergent has the following composition:

14 parts of sodium dodecylbenzenesulfonate 2.3 parts of a condensation product with a molecular weight of 8,000, produced by the addition of ethylene oxide to a polypropyleneglycol having a molecular weight between 1,500 and 1,800 2 parts of a fatty acid mixture containing 60 percent of tallow fatty acid and 40 percent of a C to C fatty acid. 48 parts of pentasodium tripolyphosphate 10 parts of sodium silicate (Na O:SiO,-=1 :2) 23.7 parts of sodium sulfate and water. No excess foaming of the washing liquor occurred and the stains were completely removed.

EXAMPLE 1 34.5 percent ofC to C fatty alcohol (JZ 5) alkoxylated with 30 moles of E0. then with 30 moles of PrO (Product A); 34.5 percent ofC to C, fatty alcohol (12 5S) alkoxylated with 2 moles of E0 (Product B);

5 percent of sodium xylenesulfonate 7 percent of acetone 7 percent of ethanol 7 percent of methylcyclohexane 5 percent of water viscosity 50 cP EXAMPLE 2 35 percent of Product A 35 percent of Product 8 5 percent of sodium xylenesult'onate 7 percent of acetone 7 percent of ethanol 6 percent of methoxycthanol 5 percent of water viscosity 46 cP EXAMPLE 3 42.8 percent of Product A 42.8 percent of Product B 4.8 percent of sodium xylcnesulfonate 4.8 percent of isopropanol 4.8 percent of water viscosity 194 cP EXAMPLE 4 27.0 percent of Product A 27.0 percent of Product B 5.0 percent of sodium xylenesulfonate 25.0 percent of ethanol l0.0 percent of ethylacetate 8.0 percent of water viscosity 30 cP As indicated each of the low-foaming, spot-removing compositions of the examples removed the stains from the soiled fabric completely without development of excessive foaming in the washing liquor.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art can be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. Liquid, low'foaming, spot-removing agents consisting of A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula wherein R, represents a straight-chained alkyl having from 16 to 24 carbon atoms, and x and y represent integers of from 20 to 40,

kyl

B. from 25 percent to 45 percent by weight of a substantially water-insoluble compound of the formula R (O-CH,CH OH C. from 2 percent to percent by weight of a hydrotropic wherein alkyl represents a straight-chained alkyl having from 18 to 22 carbon atoms and x and y represent integers of from 25 to 35,

B. from 25 percent to 45 percent by weight of a substantially water-insoluble compound of the formula alkyl-(O-Cl-l -CH ),-OH

alkali metal salt of an alkylated benzenesuifonate the 10 wherein alkyl represents a straight-chained alkyl having from alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms,

D. from 1 percent to 10 percent by weight of water, and

E. from 5 percent to 30 percent by weight of organic solvents having boiling points between temperatures of 50 C. and 350 C., selected from the group consisting of alkanols, phenylalkanols, diethylene glycol, monomethyl and monoethyl ethers of ethylene and propylene glycol, glycerine diethyl ether, mono-, diand triethanolamines, acetone, methylethylketone, cyclohexanone, dipropyl ether, diisopropyl ether, diisobutyl ether, ethyl acetate, propyl acetate, ethylene glycol diacetate, aliphatic hydrocarbons, aromatic hydrocarbons, methylcyclohexane, tetraline, decaline, chlorinated hydrocarbons, and mixtures thereof, the amount of said organic solvents being selected whereby said liquid, low-foaming, spotremoving agent has a viscosity not exceeding 500 cP at a temperature of 20 C.

2. The spot-removing agents of claim 1 wherein R represents an alkyl having from 18 to 22 carbon atoms and x and y represent integers of from 25 to 35.

3. The spot-removing agents of claim 1 wherein R, is an al- 4. Liquid, low-foaming, spot-removing agents consisting of A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula 16 to 18 carbon atoms and 1 represents an integer of from 1 to 4.5,

C. from 4 percent to 7 percent by weight of a hydrotropic alkali metal salt of an alkylated benzenesulfonate, the alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms,

D. from 1 percent to 10 percent by weight of water, and

E. from 5 percent to 30 percent by weight of a mixture of organic solvents having boiling points between temperatures of 50 C. and 350 C., selected from the group consisting of alkanols, phenylalkanols, diethyleneglycol, monomethyl and monoethyl ethers of ethylene and propylene glycol, glycerine diethyl ether, mono-, diand triethanolamines, acetone, methylethylketone, cyclohexanone, dipropylether, diisopropylether, diisobutylether, ethyl acetate, propyl acetate, ethyleneglycol diacetate, aliphatic hydrocarbons, aromatic hydrocarbons, methylcyclohexane, tetraline, decaline, chlorinated hydrocarbons and mixtures thereof, the amount of said mixture of organic solvents being selected whereby said liquid, lowfoaming, spot-removing agent has a viscosity not exceeding 500 c? at a temperature of20 C.

5. The spot-removing agents of claim 1 wherein said organic solvent is a mixture of organic solvents having boiling points between the temperatures of 50 C. and 350 C. 

2. The spot-removing agents of claim 1 wherein R1 represents an alkyl having from 18 to 22 carbon atoms and x and y represent integers of from 25 to
 35. 3. The spot-removing agents of claim 1 wherein R2 is an alkyl.
 4. Liquid, low-foaming, spot-removing agents consisting of A. from 25 percent to 45 percent by weight of a water-soluble compound of the formula wherein alkyl represents a straight-chained alkyl having from 18 TO 22 carbon atoms and x and y represent integers of from 25 to 35, B. from 25 percent to 45 percent by weight of a substantially water-insoluble compound of the formula alkyl-(O-CH2-CH2)z-OH wherein alkyl represents a straight-chained alkyl having from 16 to 18 carbon atoms and z represents an integer of from one to 4.5, C. from 4 percent to 7 percent by weight of a hydrotropic alkali metal salt of an alkylated benzenesulfonate, the alkyl groups in said alkylated benzenesulfonate having from one to three carbon atoms, D. from 1 percent to 10 percent by weight of water, and E. from 5 percent to 30 percent by weight of a mixture of organic solvents having boiling points between temperatures of 50* C. and 350* C., selected from the group consisting of alkanols, phenylalkanols, diethyleneglycol, monomethyl and monoethyl ethers of ethylene and propylene glycol, glycerine diethyl ether, mono-, di- and triethanolamines, acetone, methylethylketone, cyclohexanone, dipropylether, diisopropylether, diisobutylether, ethyl acetate, propyl acetate, ethyleneglycol diacetate, aliphatic hydrocarbons, aromatic hydrocarbons, methylcyclohexane, tetraline, decaline, chlorinated hydrocarbons and mixtures thereof, the amount of said mixture of organic solvents being selected whereby said liquid, low-foaming, spot-removing agent has a viscosity not exceeding 500 cP at a temperature of 20* C.
 5. The spot-removing agents of claim 1 wherein said organic solvent is a mixture of organic solvents having boiling points between the temperatures of 50* C. and 350* C. 